Novel chiral derivatization reagents possessing a pyridylthiourea structure for enantiospecific determination of amines and carboxylic acids in high-throughput liquid chromatography and electrospray-ionization mass spectrometry for chiral metabolomics identification

Nagao, Ryuji; Tsutsui, Haruhito; Mochizuki, Toshiki; Takayama, Tadateru; Kuwabara, Tomohiro; Min, Jun Zhe; Inoue, Kōichi; Todoroki, Kenichiro; Toyo’oka, Toshimasa

doi:10.1016/j.chroma.2013.03.019

Cited by 42 publications

(17 citation statements)

References 21 publications

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“…In addition, the enantiomers of a mixture of five β-blockers were separated in gradient elution in <3 min, with resolution values (Rs) >1.50. The overall selectivity was always sufficient [20] to avoid peak interference between the analytes of interest and by-products of the derivatization procedure ( Figure 2).…”

Section: Enantioselective Uhplc By Indirect Approachmentioning

confidence: 99%

“…also reported the use of an UHPLC method based on derivatization to improve selectivity in the determination of D-amino acid in serum, plasma, and urine [19]. Specific derivatizing agents (namely, (R)-N-(3-pyridylthiocarbamoyl)pyrrolidine-2-carboxylic acid and (S)-3-amino-1-(3-pyridylthiocarbamoyl)pyrrolidine) were developed by Nagao et al to improve the UHPLC-MS determination of chiral amines and carboxylic acids for chiral metabolomics identification [20]. As model study, racemic amino acid methyl esters and N-acetyl-DL-amino acids were identified in human saliva with highly sensitive detection at the sub-fmol level by selected reaction monitoring.…”

Section: Enantioselective Uhplc By Indirect Approachmentioning

confidence: 99%

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Enantioselective ultra high performance liquid and supercritical fluid chromatography: The race to the shortest chromatogram

Ciogli

Ismail

Mazzoccanti

et al. 2018

J of Separation Science

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The ever-increasing need for enantiomerically pure chiral compounds has greatly expanded the number of enantioselective separation methods available for the precise and accurate measurements of the enantiomeric purity. The introduction of chiral stationary phases for liquid chromatography in the last decades has revolutionized the routine methods to determine enantiomeric purity of chiral drugs, agrochemicals, fragrances, and in general of organic and organometallic compounds. In recent years, additional efforts have been placed on faster, enantioselective analytical methods capable to fulfill the high throughput requirements of modern screening procedures. Efforts in this field, capitalizing on improved chromatographic particle technology and dedicated instrumentation, have led to highly efficient separations that are routinely completed on the seconds time scale. An overview of the recent achievements in the field of ultra-high-resolution chromatography on column packed with chiral stationary phases, both based on sub-2 μm fully porous and sub-3 μm superficially porous particles, will be given, with an emphasis on very recent studies on ultrafast chiral separations.

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Section: Enantioselective Uhplc By Indirect Approachmentioning

confidence: 99%

Section: Enantioselective Uhplc By Indirect Approachmentioning

confidence: 99%

Enantioselective ultra high performance liquid and supercritical fluid chromatography: The race to the shortest chromatogram

Ciogli

Ismail

Mazzoccanti

et al. 2018

J of Separation Science

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“…The free fatty acids and cholic acids in plasma were easily identified by the mass spectra and quantified by the multiple reaction monitoring (MRM) chromatograms. 90) 3. CHIRAL DERIVATIZATION REAGENTS FOR MS/ MS ANALYSIS SPTPP and APBQ seem to be suitable derivatization reagents for amines and carboxylic acids, respectively.…”

Section: Derivatization Reagents For Amines and Carboxyls In Lc-ms/msmentioning

confidence: 99%

Diagnostic Approach to Disease Using Non-invasive Samples Based on Derivatization and LC-ESI-MS/MS

Toyo’oka

2016

Biological & Pharmaceutical Bulletin

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The determination of biologically-active molecules is very important in order to understand biological functions. A novel approach for the highly sensitive and specific determination seems to be essential for this purpose. Based on this consideration, we synthesized various types of fluorogenic and fluorescent reagents for the derivatization of chiral and achiral molecules. The fluorescence analysis is excellent for the analysis of target molecules and generally provides good expected results. However, the trace analysis of the bioactive molecules in complex matrices, such as plasma and urine, is not always satisfactory even using high-performance fluorometry. In such a situation, mass spectrometry (MS) is another technique for the selective and sensitive determination of biological components. Therefore, various derivatization reagents for MS/MS detection were developed and used for the determination of amines and carboxyls including chiral molecules. These newly developed reagents were also adopted for the biomarker detection related to diseases using non-invasive samples (i.e., saliva, nail, hair). Although the determination of the targeted chiral molecules is relatively easy, it is very difficult to identify and/or determine the enantiomeric biomarker in real samples. To solve this difficulty, we proposed the strategy called "chiral metabolomics," which means the total analysis of the enantiomers of various chiral metabolites in complex matrices. This review paper focused on the development of various new derivatization reagents for amines and carboxyls by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis and the detection of the biomarker candidates related to several diseases in non-invasive samples (i.e., hair, nail, saliva) using these reagents.

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“…83 As the ideal labeling reagents for the enantioseparation, chiral compounds possessing a pyridylthiourea structure were developed. 82 (R)-N-(3-Pyridylthiocarbamoyl)pyrrolidine-2-carboxylic acid ((R)-PyT-C) and (S)-3-amino-1-(3-pyridylthiocarbamoyl)pyrrolidine ((S)-PyT-N) are chiral reagents for enantiomeric determination of chiral amines and carboxylic acids in high-throughput LC-ESI-MS/MS, respectively. The chiral amines and carboxylic acids were respectively labeled with (R)-PyT-C and (S)-PyT-N at 60 C for 60 min in the presence of DPDS and TPP as activation reagents.…”

Section: Reagents For Chiral Amines and Carboxylic Acidsmentioning

confidence: 99%

“…The ideal reagent has to possess (1) a chiral recognition moiety, (2) a highly sensitive detection moiety (i.e., positively-charged moiety or the structure of easy protonation), (3) a moderate molecular mass suitable for tandem quadrupole MS/MS analysis, (4) a high reactivity to the target compound, and (5) the same cleavage position in the derivatives suitable for SRM. As the derivatization reagents possessing these properties, several chiral compounds were synthesized and used for the enantiometric determination of chiral amines 82 and carboxylic acids. 83 As the ideal labeling reagents for the enantioseparation, chiral compounds possessing a pyridylthiourea structure were developed.…”

Section: Reagents For Chiral Amines and Carboxylic Acidsmentioning

confidence: 99%

Derivatization-based High-throughput Bioanalysis by LC-MS

Toyo’oka

2017

ANAL. SCI.

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Liquid chromatography coupled with mass spectrometry (LC-MS) is one of the most prominent analytical techniques due to its inherent selectivity and sensitivity. LC-MS is currently the first choice for high-throughput bioanalysis due to the advancements in MS instruments and the analytical software. Based on this situation, we are developing various types of derivatization reagents, including chiral reagents for MS and/or MS/MS detection. These developed reagents are adopted for the detection of biomarker candidates related to diseases. The biomarker candidates include not only achiral molecules, but also chiral ones. Although determining the already-identified chiral molecules is relative easy, it is very difficult to identify and/or determine unknown enantiomer(s) in real samples. To solve this difficulty, we proposed a new strategy to identify unknown enantiomeric biomarkers related to diseases. This review paper deals with the development of derivatization reagents for amines and carboxylic acids in LC-MS analysis and their application to bioanalysis.

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Novel chiral derivatization reagents possessing a pyridylthiourea structure for enantiospecific determination of amines and carboxylic acids in high-throughput liquid chromatography and electrospray-ionization mass spectrometry for chiral metabolomics identification

Cited by 42 publications

References 21 publications

Enantioselective ultra high performance liquid and supercritical fluid chromatography: The race to the shortest chromatogram

Enantioselective ultra high performance liquid and supercritical fluid chromatography: The race to the shortest chromatogram

Diagnostic Approach to Disease Using Non-invasive Samples Based on Derivatization and LC-ESI-MS/MS

Derivatization-based High-throughput Bioanalysis by LC-MS

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